Polysulfide polymers



Patented Apr. 20, 1954 POLYSULFIDE POLYMERS Edward M. Fettes, Trenton, N. J., assignor, by

mesne assignments, :to Reconstruction Finance Corporation, Philadelphia, Pa., a. corporation of the United States No Drawing. Application'May 10, 1951, Serial No. 225,661

Claims. 1

This invention relates to polysulfide polymers and more particularly to a process whereby oertain known polysulfide compounds can be converted into polysulfide polymers characterized by the fact that they have a. predetermined and controllable number of monomeric units. The products of the invention :may include certain non-sulfur-containing reactive groups which, when present, confer upon the products various new and useful properties outlined hereafter. The present application is a continuation-inpart of .my .pr'ior application Serial No.-771,149 filed August 28, 1947, now abandoned.

Polysulfide polymers .:and .copolymers may be either linear, partially cross-linked or completely cross-linked. The linear compounds are characterized by recurring units SRS and may be symbolized by the formula H'(SRS)m(SRS) l-I. In this ,formula R. and R are radicals having a skeleton carbon structure selected from the group consisting of I J.( 3- and (J (I3 i I l designating respectively adjacent carbon atoms and carbon atoms joined to and separated by intervening structure. .a' and 'y are integers indieating the number of the respective *units and the ratio of those integers determinestheproportion of those units in the copolymers. -W-here :v or 11:0 the result is a homopolymer. The crosslinked polymers are characterized by the recurring units SRS and 5&8

wherein B. may have the same structure as indicated :for the linear polymers.

The polysulfide polymers may be divided broadly into two classes .(a) the normally solid polymers having molecular weights as .high as say 100,000 to 200,000 and (b) polymers which can be obtained by splitting those high polymers into lower polymers. The splitting may be effected i. e. in accordance with the disclosure of U. S. Patent 2,466,963 .to Patrick and Ferguson. In class (11) arethe polymers normally, i. e. vat 0., existing as flowable liquids and having'molecu- 'lar weights ranging from those of dimers up to about 15,000.

Both classes are widely use. The -high'polymers as such -or in the form .of solutions in aorganic solvents or dispersions in water-may berused for such purposes as hinders for transmission belts, linings for propane and butane gas hose, hose for paint spray equipment, high pressure a -sun ho e. :linines .io h se to: con ey asoine. oi etc... pump pistons and up i oil sl h. pumps. protective-jackets.for hi h ten n wires a d portable cables...prin ins r le s a la ke s o n wspaper p intin aske s, was e s, Pad all industries, icovers tor :conyeyor belting, balloonfabria. diaphragm ior controllers, regulators and meters. h nders, and adhesives for {use with leather. ccrkand-ie ts. s al fe p v n o of refrigerant leakage. loves .forchemical plants d paint factories. p i tin lates o use h. ks, paints. etc... :packines z q fiomplessors, ma y cialty molded nrqducts, protect ve line nd inin means .for tan s. .e cusua as th e use in refineries and. in dry leaninslesu p ent nd numerous other u es- In connection with many oi the foregoing uses, in order to d velop propertie su h as t eng h. solvent resistance. etc... to the highe er u in is necessary. Forthat u pos m lli s, pecially zinc oxide. are commonly u e .Iheliquid polymers are also extensively used, the uses mcluding protective coatings, impregnants, adhesives, caulkin b de s. fi ers, printer's rolls, pour d gaskets and joint sealers. There also, s ring is employed to transform the liquid polymers to the solidycondition, harden them and dev lop the p pert eslq st th, s lvent resistance,,eta. to the. desired degree. OX- idation iszone step .used for that purpose, various oxidizing agents including metallic peroxides being employed.

Obj ectsqofthe invention include the iollowing:

a. To mtmducepewifunctional r ups in the polymers as. hydroxyl, .carboxyl and amino groups.

b. To change the de r e-c po ymer za ion of a polymer to any desired extent, 1. e. to increase or decrease it. For example a normally solid high polymer may be softened or converted to a normally liquid polymeror .to .a monomer.

.c. To produce new classes ,and species of organic chemicalsiuseful as such .or as intermediates for conversion into. ether use pr ducts- The following exampleswill ,=illustrate the utility of the invention. V

The high polymers are usually cured by heat!- ing with metallic oxides. *For some purposes the electrical properties e. g. the dielectric constant, of the cured product or vulcanizate are impaired by the prescncepf metallic oxides therein. "By introducing new groups a different type of curing can'be effected. For example by introducing hyd ox .smuns. e WIPQXYIE 'WP wring be effected'byheating'withpclycarboxylic-acids or 'with polycarboxylic acids.

polyhydric alcohols respectively and thus a cured product can be produced free from metal oxides and having a relatively high dielectric constant.

It is frequently desirable to soften a high polymer to facilitate processing, or to convert it to a liquid polymer to secure the advantages of liquid over solid polymers.

The known liquid polysulfide polymers are polymercapto compounds and their uses are lim-- ited by the presence of mercapto groups. The

present invention makes it possible 'to replace those SH groups with other functional groups such as hydroxyl, carboxyl, nitrile, nitro, amino,

carbonyl and aldehyde and thus new classes and species of organic chemicals or intermediates are obtained. They may be used as such as plasticizers, oil additives, fungicides and insecticides and for other applications. They may also be convertpolymeric dimercaptan having the formula (0.) H(SC2H4S)30H where 12:30

and that it is desired to convert it into a product having the formula ed into other new and useful products including new resins, elastomers and plastics. The hydroxyl compounds constitute'new glycols or polyhydric alcohols which produce new resins by reaction The carboxyl derivatives when reacted with glycols or polyhydric alcohols also produce new resins. The amino derivatives when reacted with dibasic acids, acid chlorides or anhydrides produce new polyamide plastics useful in making filaments.

Liquid polymers produced in accordance with the present process are particularly useful for those applications where a polysulflde polymer is desired that is free from mercaptogroups and has a fluidity falling within a relatively narrow predetermined range. In the manufacture of electrical transformers, for example, so called potting compounds are used to coat the windings and in order to secure desired penetration by the coating composition a controllable fluidity is required. Liquid polymers can be prepared by the present method that have hydroxyl terminals and the desired fluidity, and these polymers can be mixed with, for example, adipic acid, applied to the transformer windings, and the coating baked to convert the mixture to a solid layer having desirable protective properties.

Other applications wherein freedomfrom mercapto groups combined with precise fluidity control are important include liquids used in fluid drives for mechanical members, and oil additives to-reduce oxidation and increase the lubricity of lubricating oils. 7

In general the process of the present invention involves treating a polysulfide compound e. g. a, linear polymeric dimercaptan having the formula-H(SRS) I-I with a, monomeric polysulfide having the formula R'SSR. In these formulae R is a radical selected from the groups "-Z-(land 3 3- l I l I designating, respectively adjacent carbon atoms and carbon atoms connected to and separated by intervening structure; R is a, monovalent organic radical of the type listed in Table I below; 1) .is a positive integer which may vary from say. 1 to 1000 or even higher; and SS is a disulfidelinkage. I

The reaction between the polymeric dimercaptan and the monomeric disulflde is preferably carried out by maintaining a, mixture of these materials at a temperature of 25 C. to 250 C. until equilibrium has been attained and then oxidizing the reaction product to convert all mercapto groups to disulflde linkages. The molecular size of the product is controlled by controlling the in other words suppose one wishes to provide product (a) with hydroxyl terminals and to change the molecular size so that there are 20 (SC2H4S) units in the molecule instead of 30.

According to the invention product (a) is reacted at temperatures of 25 C. to 250 C. with 3&0 of a mole of dihydroxydiethyl disulflde and the amount of product (a) so reacted is equal to the unit molecular weight of the radical i. e. 92 grams of product (a) is so reacted. The reaction product is then oxidized to convert all SH groups into -SS-- linkages.

The same result can be obtained by starting with one gram mol of dimercaptoethane which contains 92 grams of the unit SCzI-LiS and reacting it with of a gram mol of dihydroxydiethyl disulflde, i. e. product (12) is thereby produced.

In other words the number of SRS- groups in the product is controlled by the mol ratio of the organic monomeric disulflde to the SRS unit of the dimercaptan. That number of --SRS- groups may be any desired number e. g. from 1 to 1000, designated as n. If the mol ratio of the monomeric disulflde to the SRS unit of the dimercaptan be fixed at l/n, the product will have n SRS groups regardless of the number of SRS units in the dimercaptan selected as starting material. v

Reference will now be made to mercapto compounds characterized by the structural units s s SRS and SRS which are designated hereafter RS3 and RS4 respectively. Such compounds include the monomeric polymercapto compounds containing three or four SH groups and condensation products thereof characterized by the above mentioned structural units. 2

Consider for example :a polymercapto compound having the general' formula:

(RS3) pHp-l-Z where p varies from 1 to 1000. .That compound is reacted with an organic monomeric disulflde according to theprocedure andprinciples above explained. The size of. the productis controlled by controlling the number of RS3 units therein and that is controlled by observing th rule that the mol ratio of theorganic monomeric disulflde to theRSs unitis agen a-s:

where n is the'desirednumber of RS: units: in the product.

reacting polymercapto; compounds characterized by the,- structural unit RS4, the number of such units in the product is controlled by observing the rule that the mol ratio of the organic; monomericv disulfide to the molecular. weight of said unit is.

where n is the number of desired RS4 units in the product.

In dealing with compounds characterized, respectively by the units RS2, RS3 and RS4 the general rule for controlling the number of said units in the product is to employ a mol ratio of the organic, monomeric disulfide to the molecular weight of said unit determined by the ratio where q is the number of sulfur atoms in said unit and n is the number of said units desired in the product.

The general formula of. the product is (RS ):1L('SR-')n -z +2 (2) Where q=2 Formula 1 above becomes According. to; the: invention product (a) is reacted at temperatures of 25 C. to 250 C. with 2n 22/40-11/20 of 2. mol of dithiodiglycollic acid and the amount of product (a) so reacted is equal to the unit molecular weight of the radical RS3 i. e. 137 grams of product (a2) is reacted. The reaction product: is; then oxidized to. convert all -SH groups into SS linkages.

The generality of organic monomeric disulfides that may be used will be clear by reference to the following Table I showing numerous specific illustrations.

Table I (a) orroimssczmon (b) HOOC.CH':SSCH:.COOH (c) CHr=CH.CH'OH.CHzSSCH:.CHOH.CH=CHa um ONE}.

(1') csmce cmssomsou-eom. (a) n-cwm-oursswcui c He -GN- (o) nocimsciriisolmssciflisczaiscimou (1a,)v Hcoo -emanatesimsseimscmcuwcone.

(a). uo-oica gliz-cmseiuisscimscmcuwdooni on; em:

(s) Nccmcu1sczH-4,ss-cimscmormon a v no-011,0momsoinissc,mscmcmcmeiii-cm Hood -011s drawn-on (w) omcoo-m-ss omcoom (CHmNOSsOM-om (1 cmouc1=euceassomefl=ene-icHt OHaCHaO j-SS- OGH'JQH:

w)- Ho-oc -orrcmssomen ooou' IEH: rim

(00) OH;- on:

cmomt irr-ss iuomen= (rm onscmomom ss cmcmomcm (ii) (cmnc-ss-cwrm; (j CHH'Ii-i-iSS'C'IIIHim-H 'n, m=-1, 2,3, 4,,etc. up to 20 and do not have to be equal Ocmom-ss-cmcmO 71 All the substances in Table I have the general formula R'SSR. In accordance with the invention the H atoms of the mercapto groups of the mercapto compounds are replaced with an R radical. The functionality of those R radicals,

as will be seen, is subject to a great deal of di- 1 versification. Thus the invention provides for the endowment of polymercapto compounds with a wide diversity of functionality and, therefore, utility.

It may be noted that the R radicals of the substances listed in Table I may or may not contain sulfur, but where they do contain sulfur the sulfur atom is spaced from the disulfide linkage. In other words the substances of Table I are monomeric disulfides wherein (a) both sulfur atoms of the disulfide linkage are connected to carbon atoms and (b) each of the carbon atoms connected to the disulfide linkage is otherwise connected only to atoms of the group consistingof carbon and hydrogen.

The monomeric organic disulfide RSSR' may be produced by any suitable method. One general method is the reaction of the corresponding R'Cl compound with an alkaline disulfide e. g. NazSz. ethyl) disulfide, may be prepared by reacting ethylene chlorhydrin with sodium disulfide; compound (b) dithiodiglycolic acid may be prepared by reacting sodium disulfide with monochloracetic acid; compound di(2 vinyl 2 hydroxyethyl) disulfide may be prepared by reacting 1-chloro-2-hydroxy butene-3 (butadiene chlorhydrin) withsodium disulfide; compound ((1) di(paranitro phenyl) disulfide maybe prepared by reacting paranitro chlorbenzene with sodium disulfide; compound '(e) di(para aminophenyl) disulfide may be prepared by reducing compound (d) to produce para aminophenyl mercaptan and oxidizing the latter to condense these groups while protecting the NH2 groups; compound (1) may be obtained by reacting allyl chloride with an alkaline disulfide; compound (9) may be obtained by reacting potassium cyanide with di(chloroethyl) disulfide; compound (h) may be obtained by reacting phenol with $2012; compound (i) may be obtained by reacting an alkaline disulfide with gammachloropropyl methyl ketone; compound.

(9) may be obtained by condensing formaldehyde with glycerine monochlorhydrin (1 chlor-2, 3 dihydroxy propane) and reacting the product with time,"

ms-on Thus compound (a) above, di (hydroxy- 111' the above list 12 varies from 1 to 1000. When p equals 1 the resulting monomeric dimercaptans' O C O CHa-SH CH: CH:

OOCH2CHz-SH (FH20COCH2-SH HO CH2C-CHzO-C O CHr-SH Y CHzO-Q O OHr-SH HS-CHaCHC 0-0 CHzCHa-SH H v HS CH:CHC 0-0 CHzCHaO CHzCHz-SH HSCHzCHCHzO-C O CHzCHzCHzCHCH:

HSCHzCHCHaO CHzCIEIa- SH H S CHaCHCHaO CHzO CHnCHz-SH ns-omonomsomcno'm-sn 7' sin sn I t nsoH,cHco-oomomo-ooonornsn v H n .se, known. .Uhemistry Chap. '10, "Organic Sulfur Com- -intermittent decantation.

-of'sodi-um s-ulfi'te (Naz sm) Polymeric products of the substances shown in 'TableslIII and IV may be 'used. The polymeric dimercaptans (where p equals 2 to 1000) can be prepared by a controlled partialoxidation of the monomeric dimercaptans or preferably by a controlled splitting of polysulfide polymers as illustrated in Processes A and B below. .All of the polymercapto compounds of the invention are -characterized by the repeating unit RS (where q is 2.3 or 4) and the general formula of said compounds'is (Rsq) pHp(q 2) +2 where p varies from 1 to 1000.

Any of various oxidizing agents can be used 'in'carrying out the oxidizing step of the present process. oxidizing agents capable of oxidizing monomercaptans to produce disulfides without further oxidation of the disulfide links are, per See for example, Gilman Organic pounds by Ralph Connor, vol. 1,'p '851, 861, and Ellis The Chemistryof Petroleum Derivatives, vol. 1, p. 433. Such oxidizing agents are suitable for oxidizing mercapto groups according to the present invention and are illustrated by materials such as iodine, alkali catalyzed gaseous oxygen, ferric chloride, lead peroxide, dilute hydrogen peroxide, sulfur, alkali and alkaline earth polysulfideahypohalides, sodium plumbite and sulfur, cupric salts, ferricyanides, peroxides, and hydroperoxides. i

In order to define accurately illustrative polymercapto polysulfides that can be used as starting materials in the present process, two examples of processes. of .making such starting materials are given below and designated Process A and Process B.

Process A To 8.4 lb. tools of sodium polysulfide of rank o'f2125 dissolved in 540 gallons of water, there are added 48 pounds of crystallized magnesium chloride and pounds of flake caustic soda. The

mixture is preferably heated to 185 F. and to it are added 8 1b. mols of dichlorodiethyl formal. The organic halide is added slowly so that a period of about one hour is consumed. During this .feed the heat of reaction is used to carry the temperature up to 210 During this time the reacting polysulfide mixture is kept .under continuous and eflicient agitation to produce a highly dispersedlatex-like reaction product. At the end of the halide feed the reaction mixture is held for minutes at 212 The latex. is washed free from soluble salts by washing with water and In order to produce a satisfactory degree orstate of. high polymerization in'the latex just described, it is desirable to employ an after treatment which comprises heatiingthe latex .in-presence'of 2 lb. mole of disulfide of sodium in the form of a 2-molar solution of that-salt. The polysulfide in polymer dispersion is then heated 30 minutes at a temperature of 185 F. after which the excess polysulfide is removed by washing and decanting. The latex is again washed twice to remove most of the soluble salts. The molecular "weight of the polymer at this point is high, i. e., of the order of 100,000 to 200,000.

The high polymer is then split or disarticulated treatment of the latex with 0.8 lb. mol of sodium hydrosulfide (Na'SH) and 4.4 lb. mols The latex is heated with agitation in the presence of these splitting salts for 60 minutes at 180 F. The latex is washed until substantially free from soluble materials. It is then caused to coagulate by the addition of an amount of acid which will produce a hydrogen ionconcentration corresponding to about a pH between 4 and 5. The agglomerated polymer produced by this acid treatment is then washed completely free from soluble salts preferably by the use of cold water.

The molecular weight of the product resulting from the above treatment is found to vary between 4000 and 5000-determined cryoscopically by solution in benzene and to have a molecular size of between 25 and units, whereas the molecular weight of the polymer prior to the splitting treatment just described was too high to be quantitatively determined by any of the ordinary methods known to the chemist for determining molecular weight. The molecular weight of that polymer may be estimated at between 100,000 and 200,000. The product produced by the splitting has the formula HSRSSR SSRSH from which it will be seen that it is essentially an organic polythiopolymercaptan.

Process B Production of a polymer having a lower molecular weight than that'produ'ced by Process A can be achieved by proceeding as in Process A down to the point where the splitting or dismemberment steps are described and then proceeding as follows:

In the instant process the splitting is carried out by the addition to the washed latex of 1.6 lb. mols of sodium hydrosulfide (NaSl-I) and 4.4 lb. mols of anhydrous sodium sulfite (NazsOa). The

- latex containing the splitting salts is heated with considerable agitation for a period of one hour at a temperature of F. The split latex is acidified directly with acetic acid without intermediate washing and the final pH of the liquid is adjusted to 4-5, after which the semi-liquid reaction polymer is washed by settling and decantthat of Process A. The molecular weight of the product of Process B is approximately 1200, corresponding to from 7-8 units.

In Processes A and B a high molecular weight polymer is first made and is then split at -SS-- linkages to produce segments having terminal ---SH groups. In these particular processes linear polymers are specifically described. However, it -wi'llbeclear that the invention is not limited to the use'of linear polymers and that the polymers used are fully coextensive with the generic defini- 1131011 thereof set forth above.

In the above Processes A and B, dichlorodiethyl formal is merely one of a large number of dihalogenated compounds that .may be used. Such compounds lead to the formation of linear polymers. 13y using a compound having three or more halogen atoms in conjunction with a compound having only two halogen atoms, a polymer having cross linkage is obtained, the extent of cross linkage depending on the ratio of polyhalogen to dihalogen compounds. This ratio may be as small as 0.01 molar per cent or as high as '10-'to'20 molar per cent or higher. When a comaerator;

1 1 "pound having three or more halogen atoms is used exclusively, then the density of cross linkage is at a maximum.

The polysulfide polymers having at least two 1 SH groups and a scope and definition as above described may be obtained by methods other than those illustrated in Processes A and B, although the splitting technique there illustrated is the preferable method. It provides a close control of molecular size of the product. For example, polymers may be obtained having an average molecular size of about 500 to 15000 and having at least two SH groups and such polymers are well adapted for reaction with a compound having the formula RSSR', although the invention in its generic aspects is not limited to the use of polymers having a particular range of molecular weight.

In order to point out more fully the nature of the present invention the following specific examples are given of illustrative methods of carrying out the invention.

Example 1 This example will illustrate the preparation of a material having as a repeating unit the group SCH2CH2OCH2OCH2CH2S-- with hydroxyl terminals and with an average molecular size of ten units. As a starting material, a polymer made as in Process A or B may be used. As stated above the exact molecular size of the starting polymer has no bearing on the molecular size of the final product. The molecular size after oxidation is controlled solely by the ratio of mols of monomeric disulfide to mols of the SRS- unit of the dimercaptan polymer.

To one unit mol of the polymeric dimercaptan produced by Process A, i. e. 166 grams there is added mol of his (Z-hydroxy-ethyl) disulfide. As each molecule of product after oxidation needs two terminals one molecule of the disulfide will supply the terminals for one molecule of product. As the ratio of mols of disulfide to the unit mol of -SRS is we therefore have mols of -SRS per mol of disulfide. The molecular size of the final product is therefore 10 units of SRS- terminated at each end by an SC2H4OH group.

The mixture is heated for one to four hours at 100 C. to insure complete reaction. The reaction product is then oxidized to remove all mercaptan groups by bubbling air through the reaction mixture for ten hours at 100 C., the air being first bubbled through ammonium hydroxide.

The product is a viscous liquid having a molecular weight of 3000 to 4000. Titration of the product with iodine solution shows it has a negligible amount of mercaptan terminals. Acetylation by the standard method using acetic anhydride and pyridine showed the hydroxyl groups to be present in the correct proportion and molecular weight determinations using the cryoscopic method in benzene corresponded closely to the predicted size of ten SRS units.

Example 2 As a starting material use a dimercaptan polymer prepared as in Process A except that dichlorodiethyl ether is used in place of dichlorodiethyl formal in the actual polymer preparation. To get a product with an average molecular size of twenty units use one unit mol of dimercaptan, i. e. 136 g. and add 1 mol of dithiodiglycollic acid. The mixture is heated for 0116.

Proceed as in Example 1 substituting di(2 hydroxybutene 3) disulfide for the di(hydroxyethyl) disulfide in the same molecular ratio.

Example 4 Proceed as in Example 1, substituting diallyl disulfide for the di(hydroxyethy1) disulfide in the same molecular ratio.

Example 5 Proceed as in Example 2 substituting bis- (paranitrophenyl) disulfide for the' di thiodiglycollic acid in the same molecular ratio.

Example 6 Proceed as in Example 2 substituting bis 2, a dinitrophenyl) disulfide for the dithioglycollic acid in the same molecular ratio.

Example 7 Proceed as in Example 2 substituting for the dithioglycollic acid 10 grams of compound (1') listed in Table I above.

Ewample 8 Proceed as in Example 2 substituting for .the dithioglycollic acid 10 grams of di(para aminophenyl) disulfide.

Example 9 Proceed as in Example 1 substituting di(4- ketopentane) disulfide for the di(hydroxyethyl) disulfide in the same molecular ratio.

In each of Examples 1 to 9 the product is a viscous liquid. Also in each of these examples there may be substituted for the dimercaptan of that example any dimercaptan having the formula H(SRS)pH where p varies from l to 1000, e. g. any of the dimeroaptans listed in Table II. In each case the weight of dimercaptan taken will be such as to provide a molar weight of the -SRS unit thereof equal to the molar weight of said unit set forth in said examples, 1. e one molecular weight of the unit +S RS-.

Example 10- Production of a product composed of RS: units and carboxyl terminals. Heat 137 grams of a product having -th formula [-'SCH2g,H.CH:S]H12 1. e. one gram molecular weight of said unit -somgnoms- '13 The product is a viscous liquid having the formula som.gn.oms-](somoH:

In Example there may be substituted any of the products listed in Table HI using the same molecular proportions of the unit R'Sa and a monomeric organic disulfide having the general formula R'SSR'. I

Example 11 '7 Proceed as in Example 1 down :to the oxidatlo step. 'Then thoroughly mix with the reaction 'product 23.9 grams of lead peroxide. This quantity of lead peroxide represents .anexcess of about 50% over that theoretically required to oxidize the mercapto groups present.

The oxidized product has a viscosity slightly greater than that of the product before oxidation, '-but is still a viscous liquidand has -.a-.molecular weight of around 3000 1704000.

Example 12 Proceed as in Example 11 but substitute for the lead peroxide '7 grams of paraquinonedioxime and 3 grams of diphenyl guanidine. The product is similar to that of Example '11.

Example 13 Proceed as iin Example 11 butsubstiti1te for the lead peroxide 4.8 grams of sulfur. .sult in the evolution of some hydrogen sulfide This will re- Which may give a .temporary softening if it is not completely eliminated during milling. If, however, the hydrogen sulfide is completely eliminated, the product will have a molecular'weight mainly in the range 3000 to 4000.

Example 14 Grams 30% hydrogen peroxide 15 Sodium hypochlorite in aqueous solution 11.8 Potassium persulfate in aqueous solution 40.5 Iodine in aqueous solution 18.9 Sulfur i 4.8

The product obtained by oxidation with any of the above materials will be substantially the same as that obtained in Example 1. In the case of iodine oxidation, the acidity of the solution may have to be controlled by use of sodium earbonate to prevent the hydriodic acid formed from attacking the formal links.

I claim:

1. Process which comprises reacting an organic polymercapto compound characterized by the unit RS where R is a radical having skeleton carbon structure selected from the group consisting of I I I I representing adjacent carbon atoms and carbon atoms separated by and joined to intervening structure respectively, q is one of the integers 2, 3 and 4, and S is a sulfur atom, each of said, sulfur atoms being connected to a difierent carbon atom :of said radical, withlan organic'monomeric disulfide having the formula R'VSSR', where R is an'organic monovalent radical, at temperatures between 25 C. and 250 C. and oxidizing the reaction product to convert vsubstantially all mercapto groups to disulfide linkages, to obtain a product having the formula where n is an integer varying from 1 to 1000 and equals the desired average number of RS; units in the product, the mol ratio of said monomeric disulfide to said RS unit being said monomeric disulfide having a disulfide linkage wherein each su'liur atom is connected to a carbon atom and each of the carbon atoms connected to the disulfide linkage is otherwise connected only to atoms of the group consisting of carbon and hydrogen atoms.

'2. Process which comprises reactingan or- "ganic polymercapto compound characterized by the unit -Rszwhere R is a radical having skeleton carbon structure selected from the group consisting' of e :a'nd i I I representing adjacent carbonatoms and carbon .atoms separated by and joined to intervening structure respectively, and S is a sulfur atom, each of said sulfur atoms being connected to a different carbon atomtof said radical, with an organic monomeric disulfide having the formula RSSR' where R is an organic monovalent radical, at temperatures between 25 C. and 250 C.

i and oxidizingthe reaction product to convert substantially all-mercapto groups to disulfide linkages to obtain a product having the formula (RS2) n(SR)z where n is an integer varying from 1 to 1000 and equals the desired average number of RS2 units in the product, the mol ratio of said monomeric disulfide to said RS2 unit being l/n, said monomeric disulfide having a disulfide linkage wherein each sulfur atom is connected to a carbon atom and each of the carbon atoms connected to the disulfide linkage is otherwise connected only to atoms of the group consisting of carbon and hydrogen atoms.

3. Process which comprises reacting an organic polymercapto compound characterized by the unit RS3 where R is a radical having skeleton carbon structure selected from the group representing adjacent carbon atoms and carbon atoms separated by and joined to intervening structure respectively, and S is a sulfur atom, each of said sulfur atoms being connected to a different carbon atom of said radical, with an organic monomeric disulfide having the formula RSSR' where R is an organic monovalent radical, at temperatures between 25 C. and 250 C. and oxidizing the reaction product to convert substantially all mercapto groups to disulfide linkages to obtain a product having the formula (RSs)n(SR)n+z where n is an integer varying from 1 to1000 and equals the desired average number of RS: units in the product, the mol ratio of said monomeric disulfide to said RS3 unit being said monomeric disulfide having a disulfide linkatoms separated by and joined to intervening structure respectively, and S is a sulfur atom each of said sulfur atoms being connected to a diiferent carbon atom of said radical, with an organic monomeric disulfidehaving the formula RSSR' where R is an organic monovalent radical at temperatures between 25 C. and 250 C. and oxidizing the reactionproduct to convert substantially all mercapto ,groups to disulfide linkages to obtain a product having the formula (RS4)1L(SR')zn+z where n isan integer varying from 1 to 1000 and equals the desired average number of RS4 units in the product the mol ratio of said monomeric disulfide to said RS4 unit being said monomeric disulfide having a disulfide linkage wherein each sulfur atom is connected to a carbon atom and each of the carbon atoms connected to the disulfide linkage is otherwise connected only to atoms of the group consisting of carbon and hydrogen atoms.

5. Process which comprises reacting an organic polymercapto compound characterized by 16 r-theun'it RS2 where R is a radical having skeleton carbon structure selected from the group consisting of representing adjacent carbon atoms and carbon atoms separated by and joined to intervening structure respectively, and S is a sulfur atom, each of said sulfur atoms being connected to a diiferent carbon atom of said radical with bis (2, 4 dinitrophenyl) disulfide at a temperature of .25 C. to 250 C. and oxidizing the reaction product to convert substantially all mercapto groups to disulfide linkages to obtain a product having the formula (Ram some:

1502 where n is an integer varying from 1 to 1000 and equals the desired average number of RS2 units, )the mol ratio of said disulfide to said RS2 unit being i/n.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,142,145 Patrick Jan. 3, 1939 2,195,380 Patrick Mar. 26, 1940 2,363,614 Patrick Nov. 28, 1944 2,429,698 Schneider Oct. 28, 1947 2,606,173 Fettes Aug. 5, 1952 OTHER REFERENCES Chizallet Revue Generale Du Cauotchouc, November 1946, pages 277-284. 

1. PROCESS WHICH COMPRISES REACTING AN ORGANIC POLYMERCAPTO COMPOUND CHARACTERIZED BY THE UNIT RSQ WHERE R IS A RADICAL HAVING SKELETON CARBON STRUCTURE SELECTED FROM THE GROUP CONSISTING OF 